US10883181B2 - Hydrogen generator - Google Patents

Hydrogen generator Download PDF

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US10883181B2
US10883181B2 US15/765,650 US201615765650A US10883181B2 US 10883181 B2 US10883181 B2 US 10883181B2 US 201615765650 A US201615765650 A US 201615765650A US 10883181 B2 US10883181 B2 US 10883181B2
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anode
chamber
cathode
anode chamber
water
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US20180305828A1 (en
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Hiroyuki TAKANAMI
Yusaku NASU
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Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
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Mitsubishi Heavy Industries Environmental and Chemical Engineering Co Ltd
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Assigned to MITSUBISHI HEAVY INDUSTRIES ENVIRONMENTAL & CHEMICAL ENGINEERING CO., LTD. reassignment MITSUBISHI HEAVY INDUSTRIES ENVIRONMENTAL & CHEMICAL ENGINEERING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NASU, Yusaku, TAKANAMI, HIROYUKI
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    • C25B1/10—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B9/08—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a hydrogen generator.
  • an ion exchange membrane solid polyelectrolyte membrane
  • An apparatus having a structure in which a cation exchange membrane that allows cations to pass therethrough is sandwiched by a cathode and an anode (electrode catalyst) formed of a platinum-based noble metal catalyst, a porous feeder, and a main electrode is described in PTL 1.
  • the advantages of this apparatus are that the resistance between electrodes is small, voltage rise does not easily occur even if the current density is increased, and the like.
  • the cation exchange membrane has strong acidity. Therefore, it is necessary to use a noble metal, such as platinum, having excellent corrosion resistance, as the electrode catalyst. Accordingly, the apparatus cost increases.
  • the anion exchange membrane is formed of an alkaline material. Accordingly, it is not necessary to use a noble metal, such as platinum, as the electrode catalyst, and an increase in apparatus cost can be suppressed.
  • hydrogen generators using the anion exchange membrane have a problem that members, such as the ion exchange membrane, and gaskets or packings used for an electrolytic cell, are likely to deteriorate as compared to the apparatus using the cation exchange membrane.
  • the invention is to provide a hydrogen generator capable of suppressing deterioration of a member constituting an electrolytic cell or an anion exchange membrane, in the hydrogen generator that generates hydrogen by electrolyzing water.
  • a hydrogen generator includes an electrolytic cell; an anion exchange membrane that divides the electrolytic cell into a cathode chamber and an anode chamber; a cathode chamber water supply part that supplies water to the cathode chamber; an anode chamber water supply part that supplies water to the anode chamber; a cathode that is provided on a cathode chamber-side surface of the anion exchange membrane; an anode that is provided on an anode chamber-side surface of the anion exchange membrane; a cathode feeder that is arranged within the cathode chamber and feeds power to the cathode; an anode feeder that is arranged within the anode chamber and feeds power to the anode; and an active oxygen reduction material that is arranged within the anode chamber and reduces active oxygen generated within the anode chamber.
  • the active oxygen reduction material may have a catalyst that promotes autolysis of the active oxygen.
  • the active oxygen can be reduced by a chemical reaction.
  • the anode feeder may have conductivity and wires arranged so as to fill an internal space of the anode chamber, and the catalyst may be arranged at an outer surface of each of the wires.
  • the autolysis catalyst can be uniformly distributed within the anode chamber.
  • the active oxygen reduction material may be supplied from a catalyst supply part that adds the catalyst to the water supplied from the anode chamber water supply part.
  • the amount of dispersion of the autolysis catalyst can be increased. Additionally, an ordinary catalyst in which the autolysis catalyst is not arranged can be used as a feeder. Additionally, the amount of the autolysis catalyst can be adjusted in accordance with to the generation situation of the active oxygen.
  • the hydrogen generator may further include a pressure adjusting part that makes the internal pressure of the cathode chamber equal to or higher than the internal pressure of the anode chamber.
  • the water inside the anode chamber containing the active oxygen can be prevented from passing through the anion exchange membrane toward the cathode chamber or oxidatively decomposing the anion exchange membrane.
  • the active oxygen reduction material that reduces the active oxygen generated in the anode chamber, it is possible to suppress deterioration such that the member constituting the electrolytic cell or the anion exchange membrane is oxidatively decomposed due to the active oxygen.
  • FIG. 1 is a schematic configuration view of hydrogen generator of a first embodiment of the invention.
  • FIG. 2 is a sectional view of an electrolytic cell of the first embodiment of the invention.
  • FIG. 3 is a perspective view of a main electrode and a cathode feeder of the first embodiment of the invention.
  • FIG. 4 is a sectional view of a wire of the first embodiment of the invention.
  • FIG. 5 is a side view the wire of the first embodiment of the invention.
  • FIG. 6 is a sectional view of the electrolytic cell of a modification example of the first embodiment of the invention.
  • FIG. 7 is a sectional view of an electrolytic cell of a second embodiment of the invention.
  • FIG. 8 is a perspective view of a hydrogen generator of a third embodiment of the invention.
  • the hydrogen generator 1 of the present embodiment includes an electrolytic cell 2 , a direct-current power source 3 , a hydrogen tank 4 into which hydrogen (H 2 ) generated in the electrolytic cell 2 is introduced, and an oxygen tank 5 into which oxygen (O 2 ) generated in the electrolytic cell 2 is introduced.
  • the hydrogen generator 1 is a device that obtains hydrogen by electrolyzing water within the electrolytic cell 2 (H 2 O pure water).
  • the electrolytic cell 2 is divided into a cathode chamber 13 and an anode chamber 14 by an anion exchange membrane 7 (alkaline ion exchange membrane).
  • anion exchange membrane 7 alkaline ion exchange membrane
  • An upper part of the cathode chamber 13 and the hydrogen tank 4 are connected together via a first treated water line 17 into which treated water containing hydrogen is introduced.
  • An upper part of the anode chamber 14 and the oxygen tank 5 are connected together via a second treated water line 18 into which treated water containing oxygen is introduced.
  • a lower part of the hydrogen tank 4 and a lower part of the cathode chamber 13 are connected together via a first circulation line 15 .
  • the first circulation line 15 functions as a cathode chamber water supply part that supplies water to the cathode chamber 13 .
  • a lower part of the oxygen tank 5 and a lower part of the anode chamber 14 are connected together via a second circulation line 16 .
  • the second circulation line 16 functions as an anode chamber water supply part that supplies water to the anode chamber 14 .
  • the electrolytic cell includes a casing 6 , the anion exchange membrane 7 , a cathode 9 formed on a surface (other surface) of the anion exchange membrane 7 on the cathode chamber 13 side, an anode 10 formed on a surface (one surface) of the anion exchange membrane 7 on the anode chamber 14 side, a plate-shaped main electrode 8 connected to the direct-current power source 3 , a cathode feeder 11 , and an anode feeder 12 .
  • the casing 6 has a side wall 22 , an upper wall 23 that seals an upper part of the electrolytic cell 2 , and a lower wall 24 with that seals a lower part of the electrolytic cell 2 .
  • the electrolytic cell 2 is divided into the cathode chamber 13 and the anode chamber 14 by the anion exchange membrane 7 .
  • the lower wall 24 is provided with water introduction holes 25 for supplying water flowing through the circulation lines 15 and 16 to the cathode chamber 13 and the anode chamber 14 .
  • the upper wall 23 is provided with a hydrogen discharge hole 26 for discharging hydrogen and water from the cathode chamber 13 .
  • An oxygen discharge hole 27 for discharging oxygen and water from the anode chamber 14 is formed in the upper wall 23 .
  • the anion exchange membrane 7 is an alkaline (basic) ion exchange membrane (electrolyte membrane) that prevents passage of cations and allows passage of anions.
  • alkaline basic
  • electrophilyte membrane electrophilic membrane
  • NEOCEPTA AHA registered trademark manufactured by ASTOM CO., LTD., or the like, can be used.
  • the cathode 9 is an electrode catalyst that is attached to the face of the anion exchange membrane 7 facing the cathode chamber 13 and has a number of holes.
  • the anode 10 is an electrode catalyst that is attached to the face of the anion exchange membrane 7 facing the anode chamber 14 and has a number of holes.
  • the cathode 9 and the anode 10 have bonding faces on the surface of the anion exchange membrane by a catalyst material and an anion exchange membrane material being kneaded. That is, the anion exchange membrane 7 is sandwiched between the cathode 9 and the anode 10 , and the anion exchange membrane 7 , the cathode 9 , and the anode 10 are integrated with each other.
  • the cathode 9 and the anode 10 are formed of transition metals, such as iron, nickel, and cobalt. That is, it is not necessary to use noble metals, such as platinum and iridium, for materials for forming the cathode 9 and the anode 10 .
  • the main electrode 8 is a plate-shaped member that is arranged adjacent to the side wall 22 , and is formed of a metal having conductivity.
  • the cathode feeder 11 is a porous feeder connected to the main electrode 8 .
  • the cathode feeder 11 is constituted of a plurality of conductive wires 20 combined together so as to fill an internal space of the cathode chamber 13 .
  • the cathode feeder 11 can be formed from a plurality of meshes made of the wires 20 combined together in a lattice pattern, and the plurality of wires 20 connecting the meshes together.
  • the meshes that form a planar shape are arranged parallel to the main electrode 8 , and the wires connecting meshes together extend in a direction orthogonal to the main electrode 8 .
  • the shape of the cathode feeder 11 is not limited to the above-mentioned shape, and the cathode feeder 11 may be a porous structure capable of filing the space of the cathode chamber 13 and allowing a liquid to pass therethrough.
  • the cathode feeder 11 may be a porous structure capable of filing the space of the cathode chamber 13 and allowing a liquid to pass therethrough.
  • a structure in which wires are entangled in the form of a non-woven fabric may be adopted.
  • a material having conductivity may be formed in the form of a sponge.
  • the shape of the anode feeder 12 is almost the same as that of the cathode feeder 11 .
  • a catalyst 21 that promotes autolysis of active oxygen, such as hydrogen peroxide (H 2 O 2 ) or ozone (O 3 ).
  • the autolysis catalyst 21 functions as an active oxygen reduction material, which reduces the active oxygen generated within the anode chamber 14 , in the anode chamber 14 .
  • An oxide of a transition metal for example, manganese (Mn), molybdenum (Mo), tungsten (W), tantalum (Ta), or the like can be used as the autolysis catalyst 21 .
  • an oxide of a rare earth element for example, lanthanum (La) can be used as the autolysis catalyst 21 .
  • a complex oxide of the transition metal or the rare earth metal can be adopted as the autolysis catalyst 21 .
  • the autolysis catalyst 21 may not be uniformly distributed in the wire 20 , and may be dispersed on an outer surface of the wire 20 as illustrated in FIG. 5 . Namely, the autolysis catalyst 21 may cover at least a portion of an outer peripheral surface of the wire 20 . However, it is preferable that the autolysis catalyst 21 , is uniformly formed on the outer peripheral surface of the wire 20 .
  • the capacity C 1 of the hydrogen tank 4 and the capacity C 2 of the oxygen tank 5 are set such that the internal pressure of the hydrogen tank 4 and the internal pressure of the oxygen tank 5 , which vary with the generation of hydrogen and oxygen, become substantially equal to each other.
  • hydrogen (H 2 ) and hydroxide ions (anions, OH ⁇ ) are generated by electrolyzing water (H 2 O) in the cathode chamber 13 .
  • water and electrons (e ⁇ ) supplied from the cathode feeder 11 react with each other to generate hydrogen.
  • the hydrogen and water that are generated in the cathode chamber 13 are introduced into the hydrogen tank 4 , and are separated into gas and liquid.
  • Hydroxide ions that are anions pass through the anion exchange membrane, and move to the anode chamber 14 .
  • oxygen (O 2 ) and water (H 2 O) are generated from the hydroxide ions.
  • the oxygen and water that are generated by the anode chamber 14 are introduced into the oxygen tank 5 , and are separated into gas and liquid.
  • hydrogen peroxide (H 2 O 2 ) and ozone (O 3 ) are generated as by-products in the anode 10 .
  • the anode feeder 12 of the present embodiment is coated with the autolysis catalyst 21 that promotes the autolysis of the active oxygen, such as hydrogen peroxide or ozone. Accordingly, autolysis of hydrogen peroxide and ozone shown in Formula (5) and (6) is promoted. 2H 2 O 2 ⁇ 2H 2 O+O 2 (5) 2O 3 ⁇ 3O 2 (6)
  • the anode feeder 12 arranged at the anode chamber 14 is coated with the catalyst 21 that promotes the autolysis of the active oxygen, it is possible to suppress deterioration such that the anion exchange membrane 7 , the casing 6 , and gaskets or packings used for the casing 6 are oxidatively decomposed due to the active oxygen, or like.
  • the anion exchange membrane is mainly formed of an organic material, and is likely to be damaged when the active oxygen, such as hydrogen peroxide or ozone, diffuses. Therefore, the autolysis of the active oxygen is promoted and thereby generation of CO is suppressed, which leads to the longer lifespan of the electrode catalyst.
  • the active oxygen such as hydrogen peroxide or ozone
  • the autolysis catalyst 21 can be uniformly distributed within the anode chamber 14 .
  • the electrode catalyst is crimped at the anion exchange membrane 7 , the electric resistance is low.
  • the energy efficiency during hydrogen generation can be enhanced. Additionally, by making the capacity of the hydrogen tank 4 greater than the capacity of the oxygen tank 5 , a pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 can be made small. That is, by making the pressure difference between the internal pressure of the hydrogen tank 4 and the internal pressure of the oxygen tank 5 , the pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 communicating these tanks through the lines can be made small.
  • the electrolytic cell 2 may have a structure in which a plurality of cathode chambers 13 and anode chambers 14 are provided within the casing 6 .
  • a structure in which the positive main electrode 8 is shared by a pair of anode chambers 14 can be adopted as in the electrolytic cell 2 of a modification example of the first embodiment of FIG. 6 .
  • the water within the hydrogen tank 4 and the oxygen tank 5 are made to circulate through the electrolytic cell 2 .
  • the invention is not limited to this.
  • the water supplied to the electrolytic cell 2 may be supplied from a separate system. Additionally, the water within the hydrogen tank 4 may be introduced into the oxygen tank 5 .
  • the anode feeder 12 of the hydrogen generator of the present embodiment is not coated by the autolysis catalyst.
  • the hydrogen generator of the present embodiment has a catalyst supply part 28 that adds autolysis catalyst powder 21 S (particulates of the autolysis catalyst) to the second circulation line 16 . Accordingly, the water to which the autolysis catalyst powder 21 S is added is supplied to the anode chamber 14 via the second circulation line 16 . In other words, the water containing the autolysis catalyst powder 21 S circulates through the anode chamber 14 and the oxygen tank 5 of the present embodiment.
  • the amount of dispersion of the autolysis catalyst can be increased.
  • the amount of the autolysis catalyst can be adjusted in accordance with to the generation situation of the active oxygen.
  • the second circulation line 16 is provided with the catalyst supply part 28 is adopted in the hydrogen generator of the present embodiment.
  • the invention is not limited to this, and the autolysis catalyst powder 21 S may be added to water from the beginning.
  • hydrogen generator 1 C of a third embodiment of the invention will be described with reference to the drawings.
  • differences from the above-described first embodiment will be mainly described, and the description of similar portions will be omitted.
  • the hydrogen generator 1 C of the present embodiment is provided with a flow rate adjusting valve 29 that regulates the flow rate of water and hydrogen flowing through the first treated water line 17 .
  • the flow rate adjusting valve 29 is a valve capable of adjusting the flow passage area of the first treated water line 17 .
  • the flow rate adjusting valve 29 functions as a pressure adjusting part that makes the internal pressure of the cathode chamber 13 equal to or higher than the internal pressure of the anode chamber 14 (refer to FIG. 6 ).
  • the flow rate adjusting valve 29 has a function of adjusting the pressure difference occurring between the cathode chamber 13 and the anode chamber 14 , and adjusts the pressure of the cathode chamber 13 to be equal to or higher than the pressure of the anode chamber 14 .
  • the electrolytic cell 2 is provided with a cathode chamber pressure measuring device 30 that measures the internal pressure of the cathode chamber 13 , and an anode chamber pressure measuring device 31 that measures the internal pressure of the anode chamber 14 .
  • the hydrogen generator 1 C of the present embodiment includes a control device 32 that adjusts the flow rate adjusting valve 29 .
  • the value of the internal pressure of the cathode chamber 13 and the value of the internal pressure of the anode chamber 14 which are measured by the cathode chamber pressure measuring device 30 and the anode chamber pressure measuring device 31 , are input to the control device 32 .
  • the control device 32 adjusts the flow rate adjusting valve 29 such that the internal pressure of the cathode chamber 13 becomes equal to or higher than the internal pressure of the anode chamber 14 .
  • the capacity of the hydrogen tank 4 is greater than the capacity of the oxygen tank 5 , the pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 is small.
  • the flow passage area of the first treated water line 17 can be made small using the flow rate adjusting valve 29 .
  • the internal pressure of the cathode chamber 13 upstream of the flow rate adjusting valve 29 can be made equal to or higher than that of the anode chamber 14 .
  • the water inside the anode chamber 14 containing the active oxygen can be prevented from passing through the anion exchange membrane 7 toward the cathode chamber 13 or oxidatively decomposing the anion exchange membrane 7 .
  • the capacity of the hydrogen tank 4 and the capacity of the oxygen tank 5 are set so as to make the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 substantially equal to each other, the pressure difference occurring in the cathode chamber 13 and the anode chamber 14 can be easily adjusted by the adjustment of the flow rate adjusting valve 29 .
  • the internal pressure of the cathode chamber 13 is made higher in a state where the capacity of the hydrogen tank 4 is made greater than the capacity of the oxygen tank 5 and the pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 is made small.
  • the invention is not limited to this. That is, the internal pressure of the cathode chamber 13 may be easily raised, for example, by making the capacity of the hydrogen tank 4 and the capacity of the oxygen tank substantially equal to each other with no need for making the capacity of the hydrogen tank 4 greater than the capacity of the oxygen tank 5 .

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Abstract

Provided is a hydrogen generator which is provided with: an electrolytic cell; an anion exchange membrane which divides the electrolytic cell into a cathode chamber and an anode chamber; a cathode chamber water supply part which supplies water to the cathode chamber; an anode chamber water supply part which supplies water to the anode chamber; a cathode that is provided on the cathode chamber-side surface of the anion exchange membrane; an anode that is provided on the anode chamber-side surface of the anion exchange membrane; a cathode feeder that is arranged within the cathode chamber and feeds power to the cathode; an anode feeder that is arranged within the anode chamber and feeds power to the anode; and an active oxygen reduction material that is arranged within the anode chamber and reduces active oxygen generated within the anode chamber.

Description

TECHNICAL FIELD
The present invention relates to a hydrogen generator.
Priority is claimed on Japanese Patent Application No. 2015-206216, filed Oct. 20, 2015, the content of which is incorporated herein by reference.
BACKGROUND ART
As apparatuses that electrolyze water to generate hydrogen, apparatuses using an ion exchange membrane (solid polyelectrolyte membrane) as an electrolyte are known. An apparatus having a structure in which a cation exchange membrane that allows cations to pass therethrough is sandwiched by a cathode and an anode (electrode catalyst) formed of a platinum-based noble metal catalyst, a porous feeder, and a main electrode is described in PTL 1. The advantages of this apparatus are that the resistance between electrodes is small, voltage rise does not easily occur even if the current density is increased, and the like.
Meanwhile, in the above related-art apparatus, the cation exchange membrane has strong acidity. Therefore, it is necessary to use a noble metal, such as platinum, having excellent corrosion resistance, as the electrode catalyst. Accordingly, the apparatus cost increases.
In contrast, in recent years, apparatuses adopting an anion exchange membrane that allows anions to pass therethrough as the ion exchange membrane have been developed. The anion exchange membrane is formed of an alkaline material. Accordingly, it is not necessary to use a noble metal, such as platinum, as the electrode catalyst, and an increase in apparatus cost can be suppressed.
CITATION LIST Patent Literature
[PTL 1] Japanese Examined Patent Application Publication No. 58-15544
SUMMARY OF INVENTION Technical Problem
However, hydrogen generators using the anion exchange membrane have a problem that members, such as the ion exchange membrane, and gaskets or packings used for an electrolytic cell, are likely to deteriorate as compared to the apparatus using the cation exchange membrane.
The invention is to provide a hydrogen generator capable of suppressing deterioration of a member constituting an electrolytic cell or an anion exchange membrane, in the hydrogen generator that generates hydrogen by electrolyzing water.
Solution to Problem
According to a first aspect of the invention, a hydrogen generator includes an electrolytic cell; an anion exchange membrane that divides the electrolytic cell into a cathode chamber and an anode chamber; a cathode chamber water supply part that supplies water to the cathode chamber; an anode chamber water supply part that supplies water to the anode chamber; a cathode that is provided on a cathode chamber-side surface of the anion exchange membrane; an anode that is provided on an anode chamber-side surface of the anion exchange membrane; a cathode feeder that is arranged within the cathode chamber and feeds power to the cathode; an anode feeder that is arranged within the anode chamber and feeds power to the anode; and an active oxygen reduction material that is arranged within the anode chamber and reduces active oxygen generated within the anode chamber.
According to such a configuration, by providing as the active oxygen reduction material that reduces the active oxygen generated in the anode chamber, it is possible to suppress deterioration such that the member constituting the electrolytic cell or the anion exchange membrane is oxidatively decomposed due to the active oxygen.
In the above hydrogen generator, the active oxygen reduction material may have a catalyst that promotes autolysis of the active oxygen.
According to such a configuration, by promoting the autolysis of the active oxygen using the catalyst, the active oxygen can be reduced by a chemical reaction.
In the above hydrogen generator, the anode feeder may have conductivity and wires arranged so as to fill an internal space of the anode chamber, and the catalyst may be arranged at an outer surface of each of the wires.
According to such a configuration, by coating the wires arranged so as to fill the internal space of the anode chamber with the catalyst, the autolysis catalyst can be uniformly distributed within the anode chamber.
In the hydrogen generator, the active oxygen reduction material may be supplied from a catalyst supply part that adds the catalyst to the water supplied from the anode chamber water supply part.
According to such a configuration, the amount of dispersion of the autolysis catalyst can be increased. Additionally, an ordinary catalyst in which the autolysis catalyst is not arranged can be used as a feeder. Additionally, the amount of the autolysis catalyst can be adjusted in accordance with to the generation situation of the active oxygen.
The hydrogen generator may further include a pressure adjusting part that makes the internal pressure of the cathode chamber equal to or higher than the internal pressure of the anode chamber.
According to such a configuration, by making the internal pressure of the cathode chamber higher than the internal pressure of the anode chamber, the water inside the anode chamber containing the active oxygen can be prevented from passing through the anion exchange membrane toward the cathode chamber or oxidatively decomposing the anion exchange membrane.
Advantageous Effects of Invention
According to the invention, by providing the active oxygen reduction material that reduces the active oxygen generated in the anode chamber, it is possible to suppress deterioration such that the member constituting the electrolytic cell or the anion exchange membrane is oxidatively decomposed due to the active oxygen.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic configuration view of hydrogen generator of a first embodiment of the invention.
FIG. 2 is a sectional view of an electrolytic cell of the first embodiment of the invention.
FIG. 3 is a perspective view of a main electrode and a cathode feeder of the first embodiment of the invention.
FIG. 4 is a sectional view of a wire of the first embodiment of the invention.
FIG. 5 is a side view the wire of the first embodiment of the invention.
FIG. 6 is a sectional view of the electrolytic cell of a modification example of the first embodiment of the invention.
FIG. 7 is a sectional view of an electrolytic cell of a second embodiment of the invention.
FIG. 8 is a perspective view of a hydrogen generator of a third embodiment of the invention.
 DESCRIPTION OF EMBODIMENTS First Embodiment
Hereinafter, a hydrogen generator 1 of a first embodiment of the invention will be described in detail with reference to the drawings.
As illustrated in FIG. 1, the hydrogen generator 1 of the present embodiment includes an electrolytic cell 2, a direct-current power source 3, a hydrogen tank 4 into which hydrogen (H2) generated in the electrolytic cell 2 is introduced, and an oxygen tank 5 into which oxygen (O2) generated in the electrolytic cell 2 is introduced. The hydrogen generator 1 is a device that obtains hydrogen by electrolyzing water within the electrolytic cell 2 (H2O pure water).
The electrolytic cell 2 is divided into a cathode chamber 13 and an anode chamber 14 by an anion exchange membrane 7 (alkaline ion exchange membrane).
An upper part of the cathode chamber 13 and the hydrogen tank 4 are connected together via a first treated water line 17 into which treated water containing hydrogen is introduced. An upper part of the anode chamber 14 and the oxygen tank 5 are connected together via a second treated water line 18 into which treated water containing oxygen is introduced.
A lower part of the hydrogen tank 4 and a lower part of the cathode chamber 13 are connected together via a first circulation line 15. The first circulation line 15 functions as a cathode chamber water supply part that supplies water to the cathode chamber 13. A lower part of the oxygen tank 5 and a lower part of the anode chamber 14 are connected together via a second circulation line 16. The second circulation line 16 functions as an anode chamber water supply part that supplies water to the anode chamber 14.
As illustrated in FIG. 2, the electrolytic cell includes a casing 6, the anion exchange membrane 7, a cathode 9 formed on a surface (other surface) of the anion exchange membrane 7 on the cathode chamber 13 side, an anode 10 formed on a surface (one surface) of the anion exchange membrane 7 on the anode chamber 14 side, a plate-shaped main electrode 8 connected to the direct-current power source 3, a cathode feeder 11, and an anode feeder 12.
The casing 6 has a side wall 22, an upper wall 23 that seals an upper part of the electrolytic cell 2, and a lower wall 24 with that seals a lower part of the electrolytic cell 2.
The electrolytic cell 2 is divided into the cathode chamber 13 and the anode chamber 14 by the anion exchange membrane 7. The lower wall 24 is provided with water introduction holes 25 for supplying water flowing through the circulation lines 15 and 16 to the cathode chamber 13 and the anode chamber 14. The upper wall 23 is provided with a hydrogen discharge hole 26 for discharging hydrogen and water from the cathode chamber 13. An oxygen discharge hole 27 for discharging oxygen and water from the anode chamber 14 is formed in the upper wall 23.
The anion exchange membrane 7 is an alkaline (basic) ion exchange membrane (electrolyte membrane) that prevents passage of cations and allows passage of anions. As the anion exchange membrane 7, for example, NEOCEPTA AHA (registered trademark) manufactured by ASTOM CO., LTD., or the like, can be used.
The cathode 9 is an electrode catalyst that is attached to the face of the anion exchange membrane 7 facing the cathode chamber 13 and has a number of holes. The anode 10 is an electrode catalyst that is attached to the face of the anion exchange membrane 7 facing the anode chamber 14 and has a number of holes. The cathode 9 and the anode 10 have bonding faces on the surface of the anion exchange membrane by a catalyst material and an anion exchange membrane material being kneaded. That is, the anion exchange membrane 7 is sandwiched between the cathode 9 and the anode 10, and the anion exchange membrane 7, the cathode 9, and the anode 10 are integrated with each other.
The cathode 9 and the anode 10 are formed of transition metals, such as iron, nickel, and cobalt. That is, it is not necessary to use noble metals, such as platinum and iridium, for materials for forming the cathode 9 and the anode 10.
The main electrode 8 is a plate-shaped member that is arranged adjacent to the side wall 22, and is formed of a metal having conductivity.
The cathode feeder 11 is a porous feeder connected to the main electrode 8. As illustrated in FIG. 3, the cathode feeder 11 is constituted of a plurality of conductive wires 20 combined together so as to fill an internal space of the cathode chamber 13. For example, the cathode feeder 11 can be formed from a plurality of meshes made of the wires 20 combined together in a lattice pattern, and the plurality of wires 20 connecting the meshes together. The meshes that form a planar shape are arranged parallel to the main electrode 8, and the wires connecting meshes together extend in a direction orthogonal to the main electrode 8.
The shape of the cathode feeder 11 is not limited to the above-mentioned shape, and the cathode feeder 11 may be a porous structure capable of filing the space of the cathode chamber 13 and allowing a liquid to pass therethrough. For example, a structure in which wires are entangled in the form of a non-woven fabric may be adopted. Additionally, a material having conductivity may be formed in the form of a sponge.
The shape of the anode feeder 12 is almost the same as that of the cathode feeder 11.
As illustrated in FIG. 4, at least a portion of an outer surface of a wire 20 that constitutes the anode feeder 12 is coated with a catalyst 21 (autolysis catalyst) that promotes autolysis of active oxygen, such as hydrogen peroxide (H2O2) or ozone (O3).
The autolysis catalyst 21 functions as an active oxygen reduction material, which reduces the active oxygen generated within the anode chamber 14, in the anode chamber 14. An oxide of a transition metal, for example, manganese (Mn), molybdenum (Mo), tungsten (W), tantalum (Ta), or the like can be used as the autolysis catalyst 21. Alternatively, an oxide of a rare earth element, for example, lanthanum (La) can be used as the autolysis catalyst 21. Moreover, a complex oxide of the transition metal or the rare earth metal can be adopted as the autolysis catalyst 21.
In addition, if cost is taken into consideration, it is not preferable to use platinum (Pt) or iridium (Ir) as a material for forming the autolysis catalyst 21.
Additionally, the autolysis catalyst 21 may not be uniformly distributed in the wire 20, and may be dispersed on an outer surface of the wire 20 as illustrated in FIG. 5. Namely, the autolysis catalyst 21 may cover at least a portion of an outer peripheral surface of the wire 20. However, it is preferable that the autolysis catalyst 21, is uniformly formed on the outer peripheral surface of the wire 20.
The ratio of the capacity C1 of the hydrogen tank 4 to the capacity C2 of the oxygen tank 5 is C1:C2=2±0.5:1. That is, the capacity of the hydrogen tank 4 is set so as become greater than the capacity of the oxygen tank 5.
Specifically, the capacity C1 of the hydrogen tank 4 and the capacity C2 of the oxygen tank 5 are set such that the internal pressure of the hydrogen tank 4 and the internal pressure of the oxygen tank 5, which vary with the generation of hydrogen and oxygen, become substantially equal to each other.
That is, the ratio of the volume V1 of hydrogen generated in the cathode 9 to the volume V2 of oxygen generated in the anode 10 is V1:V2=2:1. Since the volume V1 of hydrogen is about twice the volume V2 of oxygen, a pressure difference between the internal pressure of the hydrogen tank 4 and the internal pressure of the oxygen tank 5 becomes small by increasing the capacity of the hydrogen tank 4.
Next, the operation of the hydrogen generator 1 of the present embodiment will be described.
If power is supplied to the main electrode 8 in a state where water is supplied from the circulation lines and the water has flowed into the cathode chamber 13 and the anode chamber 14, the water within the cathode chamber 13 is electrolyzed.
In the cathode chamber 13, a reaction as shown in Formula (1) as a forward reaction R1 (refer to FIG. 2) occurs.
4H2O+4e −→2H2+4OH−  (1)
That is, hydrogen (H2) and hydroxide ions (anions, OH−) are generated by electrolyzing water (H2O) in the cathode chamber 13. In other words, water and electrons (e−) supplied from the cathode feeder 11 react with each other to generate hydrogen. The hydrogen and water that are generated in the cathode chamber 13 are introduced into the hydrogen tank 4, and are separated into gas and liquid.
Hydroxide ions that are anions pass through the anion exchange membrane, and move to the anode chamber 14.
In the anode chamber 14, a reaction as shown in Formula (2) as a forward reaction R1 occurs.
4OH−→O2+2H2O+2e −  (2)
That is, oxygen (O2) and water (H2O) are generated from the hydroxide ions. The oxygen and water that are generated by the anode chamber 14 are introduced into the oxygen tank 5, and are separated into gas and liquid.
Meanwhile, in the anode chamber 14, reactions as shown in Formulas (3) and (4) as side reactions R2 (refer to FIG. 2) occurs.
2OH−→H2O2+2e −  (3)
2OH−+O2→O3+H2O+2e −  (4)
That is, hydrogen peroxide (H2O2) and ozone (O3) are generated as by-products in the anode 10.
Here, the anode feeder 12 of the present embodiment is coated with the autolysis catalyst 21 that promotes the autolysis of the active oxygen, such as hydrogen peroxide or ozone. Accordingly, autolysis of hydrogen peroxide and ozone shown in Formula (5) and (6) is promoted.
2H2O2→2H2O+O2  (5)
2O3→3O2  (6)
According to the above embodiment, as the anode feeder 12 arranged at the anode chamber 14 is coated with the catalyst 21 that promotes the autolysis of the active oxygen, it is possible to suppress deterioration such that the anion exchange membrane 7, the casing 6, and gaskets or packings used for the casing 6 are oxidatively decomposed due to the active oxygen, or like.
Particularly, the anion exchange membrane is mainly formed of an organic material, and is likely to be damaged when the active oxygen, such as hydrogen peroxide or ozone, diffuses. Therefore, the autolysis of the active oxygen is promoted and thereby generation of CO is suppressed, which leads to the longer lifespan of the electrode catalyst.
Moreover, since CO generated by the oxidization of the organic material arranged within the electrolytic cell 2 is a poisoning component of the electrode catalyst (the cathode the anode 10), the effect obtained by the autolysis of the active oxygen being promoted is great.
Additionally, by coating the wires 20 arranged so as to fill the space of the anode chamber 14 with the catalyst 21, the autolysis catalyst 21 can be uniformly distributed within the anode chamber 14.
Additionally, since the electrode catalyst is crimped at the anion exchange membrane 7, the electric resistance is low.
Accordingly, the energy efficiency during hydrogen generation can be enhanced. Additionally, by making the capacity of the hydrogen tank 4 greater than the capacity of the oxygen tank 5, a pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 can be made small. That is, by making the pressure difference between the internal pressure of the hydrogen tank 4 and the internal pressure of the oxygen tank 5, the pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 communicating these tanks through the lines can be made small. Accordingly, an electrolytic solution of the anode/cathode chamber is transmitted through the electrode and the anion exchange membrane, a decline in current efficiency (=a phenomenon in which generated oxygen and hydrogen are moved to counter electrode chambers and are reverse-electrolyzed and return to water), and damage (=a problem that active oxygen species (H2O2 and O2) generated in the anode flow back to the anion exchange membrane to oxidatively decompose the membrane) of the anion exchange membrane are easily controlled. In addition, physical deformation or damage of the anion exchange membrane can be prevented.
In addition, the electrolytic cell 2 may have a structure in which a plurality of cathode chambers 13 and anode chambers 14 are provided within the casing 6. For example, a structure in which the positive main electrode 8 is shared by a pair of anode chambers 14 can be adopted as in the electrolytic cell 2 of a modification example of the first embodiment of FIG. 6.
Additionally, in the above embodiment, a configuration in which the water within the hydrogen tank 4 and the oxygen tank 5 are made to circulate through the electrolytic cell 2 is adopted. The invention is not limited to this. The water supplied to the electrolytic cell 2 may be supplied from a separate system. Additionally, the water within the hydrogen tank 4 may be introduced into the oxygen tank 5.
Second Embodiment
Hereinafter, a hydrogen generator of a second embodiment of the invention will be described with reference to the drawings. In addition, in the present embodiment, differences from the above-described first embodiment will be mainly described, and the description of similar portions will be omitted.
As illustrated in FIG. 7, the anode feeder 12 of the hydrogen generator of the present embodiment is not coated by the autolysis catalyst.
The hydrogen generator of the present embodiment has a catalyst supply part 28 that adds autolysis catalyst powder 21S (particulates of the autolysis catalyst) to the second circulation line 16. Accordingly, the water to which the autolysis catalyst powder 21S is added is supplied to the anode chamber 14 via the second circulation line 16. In other words, the water containing the autolysis catalyst powder 21S circulates through the anode chamber 14 and the oxygen tank 5 of the present embodiment.
According to the above embodiment, the amount of dispersion of the autolysis catalyst can be increased.
Additionally, the amount of the autolysis catalyst can be adjusted in accordance with to the generation situation of the active oxygen.
In addition, a configuration in which the second circulation line 16 is provided with the catalyst supply part 28 is adopted in the hydrogen generator of the present embodiment. However, the invention is not limited to this, and the autolysis catalyst powder 21S may be added to water from the beginning.
Third Embodiment
Hereinafter, hydrogen generator 1C of a third embodiment of the invention will be described with reference to the drawings. In addition, in the present embodiment, differences from the above-described first embodiment will be mainly described, and the description of similar portions will be omitted.
As illustrated in FIG. 8, the hydrogen generator 1C of the present embodiment is provided with a flow rate adjusting valve 29 that regulates the flow rate of water and hydrogen flowing through the first treated water line 17. The flow rate adjusting valve 29 is a valve capable of adjusting the flow passage area of the first treated water line 17. In water electrolysis, a pressure difference occurs because the volume ratio of hydrogen and oxygen generated in the cathode chamber and the anode chamber differs as 2:1. For this reason, the flow rate adjusting valve 29 functions as a pressure adjusting part that makes the internal pressure of the cathode chamber 13 equal to or higher than the internal pressure of the anode chamber 14 (refer to FIG. 6). That is, the flow rate adjusting valve 29 has a function of adjusting the pressure difference occurring between the cathode chamber 13 and the anode chamber 14, and adjusts the pressure of the cathode chamber 13 to be equal to or higher than the pressure of the anode chamber 14.
The electrolytic cell 2 is provided with a cathode chamber pressure measuring device 30 that measures the internal pressure of the cathode chamber 13, and an anode chamber pressure measuring device 31 that measures the internal pressure of the anode chamber 14.
The hydrogen generator 1C of the present embodiment includes a control device 32 that adjusts the flow rate adjusting valve 29. The value of the internal pressure of the cathode chamber 13 and the value of the internal pressure of the anode chamber 14, which are measured by the cathode chamber pressure measuring device 30 and the anode chamber pressure measuring device 31, are input to the control device 32. The control device 32 adjusts the flow rate adjusting valve 29 such that the internal pressure of the cathode chamber 13 becomes equal to or higher than the internal pressure of the anode chamber 14.
Here, since the capacity of the hydrogen tank 4 is greater than the capacity of the oxygen tank 5, the pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 is small.
According to the above embodiment, the flow passage area of the first treated water line 17 can be made small using the flow rate adjusting valve 29. As pressure loss occurs in the first treated water line 17 with the decrease in the flow passage area of the first treated water line 17, the internal pressure of the cathode chamber 13 upstream of the flow rate adjusting valve 29 can be made equal to or higher than that of the anode chamber 14.
By making the internal pressure of the cathode chamber 13 equal to or higher than the internal pressure of the anode chamber 14, the water inside the anode chamber 14 containing the active oxygen can be prevented from passing through the anion exchange membrane 7 toward the cathode chamber 13 or oxidatively decomposing the anion exchange membrane 7.
Additionally, as the capacity of the hydrogen tank 4 and the capacity of the oxygen tank 5 are set so as to make the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 substantially equal to each other, the pressure difference occurring in the cathode chamber 13 and the anode chamber 14 can be easily adjusted by the adjustment of the flow rate adjusting valve 29.
In addition, in the above embodiments, a configuration is adopted in which the internal pressure of the cathode chamber 13 is made higher in a state where the capacity of the hydrogen tank 4 is made greater than the capacity of the oxygen tank 5 and the pressure difference between the internal pressure of the cathode chamber 13 and the internal pressure of the anode chamber 14 is made small. However, the invention is not limited to this. That is, the internal pressure of the cathode chamber 13 may be easily raised, for example, by making the capacity of the hydrogen tank 4 and the capacity of the oxygen tank substantially equal to each other with no need for making the capacity of the hydrogen tank 4 greater than the capacity of the oxygen tank 5.
Although the embodiments of the invention have been described above in detail with reference to the drawings, the respective components, combinations thereof, or the like in the embodiments are exemplary. Additions, omissions, substitutions, and other modifications of the components can be made without departing from the spirit of the invention. Additionally, the invention is not limited by the embodiments, and is limited only by the scope of the claims.
REFERENCE SIGNS LIST
1: HYDROGEN GENERATOR
2: ELECTROLYTIC CELL
3: DIRECT-CURRENT POWER SOURCE
4: HYDROGEN TANK
5: OXYGEN TANK
6: CASING
7: ANION EXCHANGE MEMBRANE
8: MAIN ELECTRODE
9: CATHODE
10: ANODE
11: CATHODE FEEDER
12: ANODE FEEDER
13: CATHODE CHAMBER
14: ANODE CHAMBER
15: FIRST CIRCULATION LINE (CATHODE CHAMBER WATER SUPPLY PART)
16: SECOND CIRCULATION LINE (ANODE CHAMBER WATER SUPPLY PART)
17: FIRST TREATED WATER LINE
18: SECOND TREATED WATER LINE
20: WIRE
21: AUTOLYSIS CATALYST (ACTIVE OXYGEN REDUCTION MATERIAL)
22: SIDE WALL
23: UPPER WALL
24: LOWER WALL
25: WATER INTRODUCTION HOLE
26: HYDROGEN DISCHARGE HOLE
27: OXYGEN DISCHARGE HOLE
28: CATALYST SUPPLY PART
29: FLOW RATE ADJUSTING VALVE
30: CATHODE CHAMBER PRESSURE MEASURING DEVICE
31: ANODE CHAMBER PRESSURE MEASURING DEVICE
32: CONTROL DEVICE

Claims (4)

The invention claimed is:
1. A hydrogen generator comprising:
an electrolytic cell;
a hydrogen tank;
an oxygen tank;
an anion exchange membrane that divides the electrolytic cell into a cathode chamber and an anode chamber;
a cathode chamber water supply part that supplies a first water to the cathode chamber by circulating between the hydrogen tank and the cathode chamber;
an anode chamber water supply part that supplies a second water that is a water in a different system from that of the first water to the anode chamber by circulating between the oxygen tank and the anode chamber;
a cathode that is provided on a cathode chamber-side surface of the anion exchange membrane;
an anode that is provided on an anode chamber-side surface of the anion exchange membrane;
a cathode feeder that is arranged within the cathode chamber and feeds power to the cathode;
an anode feeder that is arranged within the anode chamber and feeds power to the anode;
an active oxygen reduction material that reduces active oxygen generated within the anode chamber by hydroxide ions that move from the cathode chamber to the anode chamber passing through the anion exchange membrane; and
a pressure adjusting part that makes an internal pressure of the cathode chamber equal to or higher than an internal pressure of the anode chamber,
wherein the first water is maintained completely separate from the second water.
2. The hydrogen generator according to claim 1,
wherein the active oxygen reduction material has a catalyst that promotes autolysis of the active oxygen.
3. The hydrogen generator according to claim 2,
wherein the anode feeder has conductivity and wires arranged so as to fill an internal space of the anode chamber, and
wherein the catalyst is arranged at an outer surface of each of the wires.
4. The hydrogen generator according to claim 2,
wherein the active oxygen reduction material is supplied from a catalyst supply part that adds the catalyst to the water supplied from the anode chamber water supply part.
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CN118147669A (en) * 2024-02-09 2024-06-07 国家能源投资集团有限责任公司 Asymmetric electrolytic cell
JP7588744B1 (en) 2024-03-15 2024-11-22 三菱重工業株式会社 Water electrolysis system, and method for adjusting pressure difference between water electrolysis cells in the water electrolysis system

Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212714A (en) 1979-05-14 1980-07-15 General Electric Company Electrolysis of alkali metal halides in a three compartment cell with self-pressurized buffer compartment
US4214958A (en) 1979-05-14 1980-07-29 General Electric Company Electrolysis of alkali metal halides in a three-compartment cell with a pressurized buffer compartment
US4294683A (en) * 1979-04-02 1981-10-13 Creusot-Loire Electrolysis unit
US4300987A (en) * 1978-04-14 1981-11-17 Tseung Alfred C C Gas extraction
US4323442A (en) * 1979-07-05 1982-04-06 Creusot-Loire Electrolysis installation for the production of gas
US4331523A (en) * 1980-03-31 1982-05-25 Showa Denko Kk Method for electrolyzing water or aqueous solutions
JPS5815544B1 (en) 1980-05-02 1983-03-26 Gen Electric
US4698144A (en) * 1986-05-15 1987-10-06 The Dow Chemical Company Apparatus for balancing electrolytic cell gas with circulating electrolyte
US4902397A (en) * 1987-06-25 1990-02-20 Imperial Chemical Industries Plc Electrolytic cell with differential gas pressure control device
US5690797A (en) * 1995-01-18 1997-11-25 Mitsubishi Corporation Hydrogen and oxygen gas generating system
JP2002028655A (en) 2000-07-19 2002-01-29 Mitsubishi Heavy Ind Ltd Electrolytic water feed method to electrolytic bath for ozone generation and ozone generation device
US20040043283A1 (en) * 2002-09-04 2004-03-04 Cipollini Ned E. Membrane electrode assemblies with hydrogen peroxide decomposition catalyst
US20040072040A1 (en) * 2002-04-23 2004-04-15 University Of Massachusetts Lowell Electrolyzer pressure equalization system
US6787258B2 (en) * 2002-03-05 2004-09-07 Vladimir Prerad Hydrogen based energy storage apparatus and method
US20050072688A1 (en) * 2003-10-02 2005-04-07 Meltser Mark A. Electrolyzer system to produce gas at high pressure
US20050186458A1 (en) * 2003-09-22 2005-08-25 Ali Rusta-Sallehy Electrolyzer cell stack system
CN1878729A (en) 2003-11-11 2006-12-13 本田技研工业株式会社 Electrolysis vessel and apparatus for generating electrolyzed water
US20070131541A1 (en) 2004-10-26 2007-06-14 Kohichi Miyashita Electrolysis vessel and apparatus for generating electrolyzed water
WO2007082898A2 (en) 2006-01-18 2007-07-26 Acta S.P.A. Catalysts for the production of hydrogen by the electrolysis of water, electrolysers in which they are used, and processes for the production of hydrogen by the electrolysis of water
JP2007284705A (en) 2006-04-12 2007-11-01 Showa Denko Kk Electrolytic hydrogen-generating device, method for generating hydrogen gas, and fuel cell
JP3139159U (en) 2007-11-20 2008-01-31 ファースト・オーシャン株式会社 Electrolyzer for water electrolysis
CN101270368A (en) 2008-05-19 2008-09-24 哈尔滨工业大学 Method for biohydrogen production by cascade utilization of organic wastewater
DE102010010905A1 (en) 2010-03-08 2011-09-08 FuMA-Tech Gesellschaft für funktionelle Membranen und Anlagentechnologie mbH Electrolytic cell useful in an electrolysis cell block, comprises an anode chamber, a cathode chamber spatially separated from the anode chamber, and a brine chamber arranged between the anode and cathode chambers
DE102011053142A1 (en) 2011-08-31 2013-02-28 Kumatec Sondermaschinenbau & Kunststoffverarbeitung Gmbh Electrolyzer, useful for generating hydrogen and oxygen by electrochemical decomposition of water, comprises housing with electrodes connected to poles of direct current supply source and separated by diaphragm, and gas separation chamber
US20130256152A1 (en) * 2010-10-14 2013-10-03 Acal Energy Ltd Cell
US20140183054A1 (en) * 2011-06-06 2014-07-03 Axine Water Technologies, Inc. Efficient treatment of wastewater using electrochemical cell
US20150157976A1 (en) * 2013-12-05 2015-06-11 Dionex Corporation Gas-less electrolytic device and method
US20150349368A1 (en) * 2014-05-29 2015-12-03 Christopher G. ARGES Reversible alkaline membrane hydrogen fuel cell-water electrolyzer
US20170244109A1 (en) * 2014-09-08 2017-08-24 Johnson Matthey Fuel Cells Limited Catalyst
US20180274110A1 (en) * 2017-03-23 2018-09-27 Kabushiki Kaisha Toshiba Laminated electrolyte membrane, membrane electrode assembly, water electrolysis cell, stack, and water electrolysis apparatus

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4300987A (en) * 1978-04-14 1981-11-17 Tseung Alfred C C Gas extraction
US4294683A (en) * 1979-04-02 1981-10-13 Creusot-Loire Electrolysis unit
US4212714A (en) 1979-05-14 1980-07-15 General Electric Company Electrolysis of alkali metal halides in a three compartment cell with self-pressurized buffer compartment
US4214958A (en) 1979-05-14 1980-07-29 General Electric Company Electrolysis of alkali metal halides in a three-compartment cell with a pressurized buffer compartment
JPS565989A (en) 1979-05-14 1981-01-22 Gen Electric Electrolysing method and apparatus of alkali metal halide
JPS565990A (en) 1979-05-14 1981-01-22 Gen Electric Electrolysis method and apparatus
US4323442A (en) * 1979-07-05 1982-04-06 Creusot-Loire Electrolysis installation for the production of gas
US4331523A (en) * 1980-03-31 1982-05-25 Showa Denko Kk Method for electrolyzing water or aqueous solutions
JPS5815544B1 (en) 1980-05-02 1983-03-26 Gen Electric
US4698144A (en) * 1986-05-15 1987-10-06 The Dow Chemical Company Apparatus for balancing electrolytic cell gas with circulating electrolyte
US4902397A (en) * 1987-06-25 1990-02-20 Imperial Chemical Industries Plc Electrolytic cell with differential gas pressure control device
US5690797A (en) * 1995-01-18 1997-11-25 Mitsubishi Corporation Hydrogen and oxygen gas generating system
JP2002028655A (en) 2000-07-19 2002-01-29 Mitsubishi Heavy Ind Ltd Electrolytic water feed method to electrolytic bath for ozone generation and ozone generation device
US6787258B2 (en) * 2002-03-05 2004-09-07 Vladimir Prerad Hydrogen based energy storage apparatus and method
US20040072040A1 (en) * 2002-04-23 2004-04-15 University Of Massachusetts Lowell Electrolyzer pressure equalization system
US20040043283A1 (en) * 2002-09-04 2004-03-04 Cipollini Ned E. Membrane electrode assemblies with hydrogen peroxide decomposition catalyst
US20050186458A1 (en) * 2003-09-22 2005-08-25 Ali Rusta-Sallehy Electrolyzer cell stack system
US20050072688A1 (en) * 2003-10-02 2005-04-07 Meltser Mark A. Electrolyzer system to produce gas at high pressure
CN1878729A (en) 2003-11-11 2006-12-13 本田技研工业株式会社 Electrolysis vessel and apparatus for generating electrolyzed water
US20070131541A1 (en) 2004-10-26 2007-06-14 Kohichi Miyashita Electrolysis vessel and apparatus for generating electrolyzed water
WO2007082898A2 (en) 2006-01-18 2007-07-26 Acta S.P.A. Catalysts for the production of hydrogen by the electrolysis of water, electrolysers in which they are used, and processes for the production of hydrogen by the electrolysis of water
JP2007284705A (en) 2006-04-12 2007-11-01 Showa Denko Kk Electrolytic hydrogen-generating device, method for generating hydrogen gas, and fuel cell
US20100270172A1 (en) 2007-11-20 2010-10-28 Ecolab Usa Inc. Electrolyzer cell for producing acidic or alkaline electrolyzed water
JP3139159U (en) 2007-11-20 2008-01-31 ファースト・オーシャン株式会社 Electrolyzer for water electrolysis
CN101270368A (en) 2008-05-19 2008-09-24 哈尔滨工业大学 Method for biohydrogen production by cascade utilization of organic wastewater
DE102010010905A1 (en) 2010-03-08 2011-09-08 FuMA-Tech Gesellschaft für funktionelle Membranen und Anlagentechnologie mbH Electrolytic cell useful in an electrolysis cell block, comprises an anode chamber, a cathode chamber spatially separated from the anode chamber, and a brine chamber arranged between the anode and cathode chambers
US20130256152A1 (en) * 2010-10-14 2013-10-03 Acal Energy Ltd Cell
US20140183054A1 (en) * 2011-06-06 2014-07-03 Axine Water Technologies, Inc. Efficient treatment of wastewater using electrochemical cell
DE102011053142A1 (en) 2011-08-31 2013-02-28 Kumatec Sondermaschinenbau & Kunststoffverarbeitung Gmbh Electrolyzer, useful for generating hydrogen and oxygen by electrochemical decomposition of water, comprises housing with electrodes connected to poles of direct current supply source and separated by diaphragm, and gas separation chamber
US20150157976A1 (en) * 2013-12-05 2015-06-11 Dionex Corporation Gas-less electrolytic device and method
US20150349368A1 (en) * 2014-05-29 2015-12-03 Christopher G. ARGES Reversible alkaline membrane hydrogen fuel cell-water electrolyzer
US20170244109A1 (en) * 2014-09-08 2017-08-24 Johnson Matthey Fuel Cells Limited Catalyst
US20180274110A1 (en) * 2017-03-23 2018-09-27 Kabushiki Kaisha Toshiba Laminated electrolyte membrane, membrane electrode assembly, water electrolysis cell, stack, and water electrolysis apparatus

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Kuznetsova et al, Identification of the byproducts of the oxygen evolution reaction of Rutile-type oxides under dynamic conditions, Journal of Electroanalytical Chemistry, vol. 728, Aug. 2014, pp. 102-111 (Year: 2014). *
Leng et al, Solid-State Water Electrolysis with an Alkaline Membrane (plus Supporting Information), Journal of the American Chemical Society, vol. 134, No. 22, May 2012, pp. 9054-9057 and S1-S13 (Year: 2012). *
PCT/ISA/210, "International Search Report for International Application No. PCT/JP2016/080686," dated Nov. 22, 2016.
PCT/ISA/237 "Written Opinion of the International Searching Authority for International Application No. PCT/JP2016/080686," dated Nov. 22, 2016.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11390956B1 (en) 2021-06-01 2022-07-19 Verdagy, Inc. Anode and/or cathode pan assemblies in an electrochemical cell, and methods to use and manufacture thereof
US11444304B1 (en) 2021-06-01 2022-09-13 Verdagy, Inc. Anode and/or cathode pan assemblies in an electrochemical cell, and methods to use and manufacture thereof
US11799110B2 (en) 2021-06-01 2023-10-24 Verdagy, Inc. Anode and/or cathode pan assemblies in an electrochemical cell, and methods to use and manufacture thereof
US12209319B2 (en) 2021-06-01 2025-01-28 Verdagy, Inc. Anode and/or cathode pan assemblies in an electrochemical cell, and methods to use and manufacture thereof
US11431012B1 (en) 2021-08-09 2022-08-30 Verdagy, Inc. Electrochemical cell with gap between electrode and membrane, and methods to use and manufacture thereof
US11670789B2 (en) 2021-08-09 2023-06-06 Verdagy, Inc. Electrochemical cell with gap between electrode and membrane, and methods to use and manufacture thereof

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CN108138341B (en) 2019-06-21
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WO2017069083A1 (en) 2017-04-27

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